EP1444239A1 - High refractive index aromatic-based silyl monomers - Google Patents
High refractive index aromatic-based silyl monomersInfo
- Publication number
- EP1444239A1 EP1444239A1 EP02786399A EP02786399A EP1444239A1 EP 1444239 A1 EP1444239 A1 EP 1444239A1 EP 02786399 A EP02786399 A EP 02786399A EP 02786399 A EP02786399 A EP 02786399A EP 1444239 A1 EP1444239 A1 EP 1444239A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomers
- aromatic
- polymeric composition
- copolymerization
- composition produced
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000000178 monomer Substances 0.000 title claims abstract description 69
- 125000003118 aryl group Chemical group 0.000 title claims abstract description 36
- 125000001181 organosilyl group Chemical group [SiH3]* 0.000 title 1
- 239000000203 mixture Substances 0.000 claims abstract description 65
- 125000003808 silyl group Chemical group [H][Si]([H])([H])[*] 0.000 claims abstract description 24
- 238000007334 copolymerization reaction Methods 0.000 claims abstract description 19
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 13
- 230000002209 hydrophobic effect Effects 0.000 claims abstract description 10
- 125000004469 siloxy group Chemical group [SiH3]O* 0.000 claims abstract description 7
- 238000000034 method Methods 0.000 claims description 15
- CERQOIWHTDAKMF-UHFFFAOYSA-M Methacrylate Chemical compound CC(=C)C([O-])=O CERQOIWHTDAKMF-UHFFFAOYSA-M 0.000 claims description 9
- -1 aromatic alkylsilane Chemical class 0.000 claims description 9
- 239000003795 chemical substances by application Substances 0.000 claims description 8
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 claims description 8
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 claims description 8
- 239000003431 cross linking reagent Substances 0.000 claims description 7
- 238000005728 strengthening Methods 0.000 claims description 7
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- 125000000217 alkyl group Chemical group 0.000 claims description 6
- 125000004104 aryloxy group Chemical group 0.000 claims description 6
- 125000000623 heterocyclic group Chemical group 0.000 claims description 6
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 5
- VVQNEPGJFQJSBK-UHFFFAOYSA-N Methyl methacrylate Chemical compound COC(=O)C(C)=C VVQNEPGJFQJSBK-UHFFFAOYSA-N 0.000 claims description 5
- 210000004087 cornea Anatomy 0.000 claims description 4
- KIUCZUZJAYXGOQ-UHFFFAOYSA-N 3-benzhydrylsilylpropyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C([SiH2]CCCOC(=O)C(=C)C)C1=CC=CC=C1 KIUCZUZJAYXGOQ-UHFFFAOYSA-N 0.000 claims description 3
- PKBZUGSITIBLFK-UHFFFAOYSA-N 3-phenylpropyl prop-2-enoate Chemical compound C=CC(=O)OCCCC1=CC=CC=C1 PKBZUGSITIBLFK-UHFFFAOYSA-N 0.000 claims description 3
- 125000003545 alkoxy group Chemical group 0.000 claims description 3
- 150000008378 aryl ethers Chemical class 0.000 claims description 3
- 125000000753 cycloalkyl group Chemical group 0.000 claims description 3
- 125000001424 substituent group Chemical group 0.000 claims description 3
- PUPZLCDOIYMWBV-UHFFFAOYSA-N (+/-)-1,3-Butanediol Chemical compound CC(O)CCO PUPZLCDOIYMWBV-UHFFFAOYSA-N 0.000 claims description 2
- 229920002818 (Hydroxyethyl)methacrylate Polymers 0.000 claims description 2
- ZXHDVRATSGZISC-UHFFFAOYSA-N 1,2-bis(ethenoxy)ethane Chemical compound C=COCCOC=C ZXHDVRATSGZISC-UHFFFAOYSA-N 0.000 claims description 2
- BJELTSYBAHKXRW-UHFFFAOYSA-N 2,4,6-triallyloxy-1,3,5-triazine Chemical compound C=CCOC1=NC(OCC=C)=NC(OCC=C)=N1 BJELTSYBAHKXRW-UHFFFAOYSA-N 0.000 claims description 2
- WDQMWEYDKDCEHT-UHFFFAOYSA-N 2-ethylhexyl 2-methylprop-2-enoate Chemical compound CCCCC(CC)COC(=O)C(C)=C WDQMWEYDKDCEHT-UHFFFAOYSA-N 0.000 claims description 2
- CEXQWAAGPPNOQF-UHFFFAOYSA-N 2-phenoxyethyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OCCOC1=CC=CC=C1 CEXQWAAGPPNOQF-UHFFFAOYSA-N 0.000 claims description 2
- IXRMMRFENFYTHQ-UHFFFAOYSA-N 3,3-diphenylpropyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C(CCOC(=O)C(=C)C)C1=CC=CC=C1 IXRMMRFENFYTHQ-UHFFFAOYSA-N 0.000 claims description 2
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 claims description 2
- 239000004641 Diallyl-phthalate Substances 0.000 claims description 2
- WOBHKFSMXKNTIM-UHFFFAOYSA-N Hydroxyethyl methacrylate Chemical compound CC(=C)C(=O)OCCO WOBHKFSMXKNTIM-UHFFFAOYSA-N 0.000 claims description 2
- DAKWPKUUDNSNPN-UHFFFAOYSA-N Trimethylolpropane triacrylate Chemical compound C=CC(=O)OCC(CC)(COC(=O)C=C)COC(=O)C=C DAKWPKUUDNSNPN-UHFFFAOYSA-N 0.000 claims description 2
- HFBMWMNUJJDEQZ-UHFFFAOYSA-N acryloyl chloride Chemical compound ClC(=O)C=C HFBMWMNUJJDEQZ-UHFFFAOYSA-N 0.000 claims description 2
- 150000005215 alkyl ethers Chemical class 0.000 claims description 2
- QUDWYFHPNIMBFC-UHFFFAOYSA-N bis(prop-2-enyl) benzene-1,2-dicarboxylate Chemical compound C=CCOC(=O)C1=CC=CC=C1C(=O)OCC=C QUDWYFHPNIMBFC-UHFFFAOYSA-N 0.000 claims description 2
- 239000003054 catalyst Substances 0.000 claims description 2
- 125000004386 diacrylate group Chemical group 0.000 claims description 2
- AFOSIXZFDONLBT-UHFFFAOYSA-N divinyl sulfone Chemical compound C=CS(=O)(=O)C=C AFOSIXZFDONLBT-UHFFFAOYSA-N 0.000 claims description 2
- XXMIOPMDWAUFGU-UHFFFAOYSA-N hexane-1,6-diol Chemical compound OCCCCCCO XXMIOPMDWAUFGU-UHFFFAOYSA-N 0.000 claims description 2
- 150000002734 metacrylic acid derivatives Chemical class 0.000 claims description 2
- SLCVBVWXLSEKPL-UHFFFAOYSA-N neopentyl glycol Chemical compound OCC(C)(C)CO SLCVBVWXLSEKPL-UHFFFAOYSA-N 0.000 claims description 2
- YODZTKMDCQEPHD-UHFFFAOYSA-N thiodiglycol Chemical compound OCCSCCO YODZTKMDCQEPHD-UHFFFAOYSA-N 0.000 claims description 2
- ZIBGPFATKBEMQZ-UHFFFAOYSA-N triethylene glycol Chemical compound OCCOCCOCCO ZIBGPFATKBEMQZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000003754 machining Methods 0.000 claims 2
- 238000005266 casting Methods 0.000 claims 1
- 239000000463 material Substances 0.000 description 17
- 239000007943 implant Substances 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 238000004519 manufacturing process Methods 0.000 description 12
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- YMWUJEATGCHHMB-UHFFFAOYSA-N Dichloromethane Chemical compound ClCCl YMWUJEATGCHHMB-UHFFFAOYSA-N 0.000 description 6
- XEKOWRVHYACXOJ-UHFFFAOYSA-N Ethyl acetate Chemical compound CCOC(C)=O XEKOWRVHYACXOJ-UHFFFAOYSA-N 0.000 description 6
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 6
- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 6
- ZSIAUFGUXNUGDI-UHFFFAOYSA-N hexan-1-ol Chemical compound CCCCCCO ZSIAUFGUXNUGDI-UHFFFAOYSA-N 0.000 description 6
- 230000000704 physical effect Effects 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 5
- 238000003786 synthesis reaction Methods 0.000 description 5
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 description 4
- JUJWROOIHBZHMG-UHFFFAOYSA-N Pyridine Chemical compound C1=CC=NC=C1 JUJWROOIHBZHMG-UHFFFAOYSA-N 0.000 description 4
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 4
- 208000002847 Surgical Wound Diseases 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- STVZJERGLQHEKB-UHFFFAOYSA-N ethylene glycol dimethacrylate Chemical compound CC(=C)C(=O)OCCOC(=O)C(C)=C STVZJERGLQHEKB-UHFFFAOYSA-N 0.000 description 4
- 239000003999 initiator Substances 0.000 description 4
- 125000001997 phenyl group Chemical group [H]C1=C([H])C([H])=C(*)C([H])=C1[H] 0.000 description 4
- 229920003229 poly(methyl methacrylate) Polymers 0.000 description 4
- 125000001436 propyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])[H] 0.000 description 4
- QOITVSZSIQMDPL-UHFFFAOYSA-N 3-benzhydrylsilylpropyl prop-2-enoate Chemical compound C=1C=CC=CC=1C([SiH2]CCCOC(=O)C=C)C1=CC=CC=C1 QOITVSZSIQMDPL-UHFFFAOYSA-N 0.000 description 3
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 3
- 229920006397 acrylic thermoplastic Polymers 0.000 description 3
- 210000002159 anterior chamber Anatomy 0.000 description 3
- 238000013461 design Methods 0.000 description 3
- 238000009472 formulation Methods 0.000 description 3
- 230000009477 glass transition Effects 0.000 description 3
- 239000000017 hydrogel Substances 0.000 description 3
- 238000003780 insertion Methods 0.000 description 3
- 230000037431 insertion Effects 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 229920001296 polysiloxane Polymers 0.000 description 3
- 238000001356 surgical procedure Methods 0.000 description 3
- ISXSCDLOGDJUNJ-UHFFFAOYSA-N tert-butyl prop-2-enoate Chemical compound CC(C)(C)OC(=O)C=C ISXSCDLOGDJUNJ-UHFFFAOYSA-N 0.000 description 3
- 238000012719 thermal polymerization Methods 0.000 description 3
- 229940124543 ultraviolet light absorber Drugs 0.000 description 3
- 125000000008 (C1-C10) alkyl group Chemical group 0.000 description 2
- WHNPOQXWAMXPTA-UHFFFAOYSA-N 3-methylbut-2-enamide Chemical compound CC(C)=CC(N)=O WHNPOQXWAMXPTA-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 2
- 208000002177 Cataract Diseases 0.000 description 2
- HEDRZPFGACZZDS-UHFFFAOYSA-N Chloroform Chemical compound ClC(Cl)Cl HEDRZPFGACZZDS-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- YLQBMQCUIZJEEH-UHFFFAOYSA-N Furan Chemical compound C=1C=COC=1 YLQBMQCUIZJEEH-UHFFFAOYSA-N 0.000 description 2
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 description 2
- 208000035965 Postoperative Complications Diseases 0.000 description 2
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 description 2
- YTPLMLYBLZKORZ-UHFFFAOYSA-N Thiophene Chemical compound C=1C=CSC=1 YTPLMLYBLZKORZ-UHFFFAOYSA-N 0.000 description 2
- NIXOWILDQLNWCW-UHFFFAOYSA-N acrylic acid group Chemical group C(C=C)(=O)O NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 description 2
- 238000007605 air drying Methods 0.000 description 2
- 239000003618 borate buffered saline Substances 0.000 description 2
- 239000012267 brine Substances 0.000 description 2
- 239000002775 capsule Substances 0.000 description 2
- 230000001886 ciliary effect Effects 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000011521 glass Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 125000001624 naphthyl group Chemical group 0.000 description 2
- 125000005186 naphthyloxy group Chemical group C1(=CC=CC2=CC=CC=C12)O* 0.000 description 2
- 239000012044 organic layer Substances 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- 229920000642 polymer Polymers 0.000 description 2
- UMJSCPRVCHMLSP-UHFFFAOYSA-N pyridine Natural products COC1=CC=CN=C1 UMJSCPRVCHMLSP-UHFFFAOYSA-N 0.000 description 2
- 230000005855 radiation Effects 0.000 description 2
- 150000003254 radicals Chemical class 0.000 description 2
- 239000000741 silica gel Substances 0.000 description 2
- 229910002027 silica gel Inorganic materials 0.000 description 2
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 2
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 150000003852 triazoles Chemical class 0.000 description 2
- 230000004304 visual acuity Effects 0.000 description 2
- GVYHLYQWXHOJGV-UHFFFAOYSA-N (1-propan-2-ylcyclopentyl) prop-2-enoate Chemical compound C=CC(=O)OC1(C(C)C)CCCC1 GVYHLYQWXHOJGV-UHFFFAOYSA-N 0.000 description 1
- RWCHFQMCWQLPAS-UHFFFAOYSA-N (1-tert-butylcyclohexyl) 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1(C(C)(C)C)CCCCC1 RWCHFQMCWQLPAS-UHFFFAOYSA-N 0.000 description 1
- HGXJDMCMYLEZMJ-UHFFFAOYSA-N (2-methylpropan-2-yl)oxy 2,2-dimethylpropaneperoxoate Chemical compound CC(C)(C)OOOC(=O)C(C)(C)C HGXJDMCMYLEZMJ-UHFFFAOYSA-N 0.000 description 1
- IMNBHNRXUAJVQE-UHFFFAOYSA-N (4-benzoyl-3-hydroxyphenyl) 2-methylprop-2-enoate Chemical compound OC1=CC(OC(=O)C(=C)C)=CC=C1C(=O)C1=CC=CC=C1 IMNBHNRXUAJVQE-UHFFFAOYSA-N 0.000 description 1
- BEQKKZICTDFVMG-UHFFFAOYSA-N 1,2,3,4,6-pentaoxepane-5,7-dione Chemical compound O=C1OOOOC(=O)O1 BEQKKZICTDFVMG-UHFFFAOYSA-N 0.000 description 1
- VAYTZRYEBVHVLE-UHFFFAOYSA-N 1,3-dioxol-2-one Chemical compound O=C1OC=CO1 VAYTZRYEBVHVLE-UHFFFAOYSA-N 0.000 description 1
- SRRPLAOQTKSJTO-UHFFFAOYSA-N 1-[dimethyl(phenyl)silyl]propyl 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC(CC)[Si](C)(C)C1=CC=CC=C1 SRRPLAOQTKSJTO-UHFFFAOYSA-N 0.000 description 1
- IJYJVLVYMXHHGS-UHFFFAOYSA-N 1-benzhydrylsilylpropyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1C([SiH2]C(OC(=O)C(C)=C)CC)C1=CC=CC=C1 IJYJVLVYMXHHGS-UHFFFAOYSA-N 0.000 description 1
- ARNKHYQYAZLEEP-UHFFFAOYSA-N 1-naphthalen-1-yloxynaphthalene Chemical compound C1=CC=C2C(OC=3C4=CC=CC=C4C=CC=3)=CC=CC2=C1 ARNKHYQYAZLEEP-UHFFFAOYSA-N 0.000 description 1
- ZQIPTRMIMDGMNB-UHFFFAOYSA-N 1-triphenylsilylpropyl 2-methylprop-2-enoate Chemical compound C=1C=CC=CC=1[Si](C=1C=CC=CC=1)(C(OC(=O)C(C)=C)CC)C1=CC=CC=C1 ZQIPTRMIMDGMNB-UHFFFAOYSA-N 0.000 description 1
- NMMXJQKTXREVGN-UHFFFAOYSA-N 2-(4-benzoyl-3-hydroxyphenoxy)ethyl prop-2-enoate Chemical compound OC1=CC(OCCOC(=O)C=C)=CC=C1C(=O)C1=CC=CC=C1 NMMXJQKTXREVGN-UHFFFAOYSA-N 0.000 description 1
- MLJSQNWRNAHEGI-UHFFFAOYSA-N 2-ethenoxyethenyl carbamate Chemical compound C(N)(OC=COC=C)=O MLJSQNWRNAHEGI-UHFFFAOYSA-N 0.000 description 1
- KMNCBSZOIQAUFX-UHFFFAOYSA-N 2-ethoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OCC)C(=O)C1=CC=CC=C1 KMNCBSZOIQAUFX-UHFFFAOYSA-N 0.000 description 1
- BQZJOQXSCSZQPS-UHFFFAOYSA-N 2-methoxy-1,2-diphenylethanone Chemical compound C=1C=CC=CC=1C(OC)C(=O)C1=CC=CC=C1 BQZJOQXSCSZQPS-UHFFFAOYSA-N 0.000 description 1
- RXWNCMHRJCOWDK-UHFFFAOYSA-N 2-naphthalen-1-ylethanol Chemical compound C1=CC=C2C(CCO)=CC=CC2=C1 RXWNCMHRJCOWDK-UHFFFAOYSA-N 0.000 description 1
- VDEYGKYGGKVVDS-UHFFFAOYSA-N 3-[3-tert-butyl-4-hydroxy-5-(5-methoxybenzotriazol-2-yl)phenoxy]propyl 2-methylprop-2-enoate Chemical compound N1=C2C=C(OC)C=CC2=NN1C1=CC(OCCCOC(=O)C(C)=C)=CC(C(C)(C)C)=C1O VDEYGKYGGKVVDS-UHFFFAOYSA-N 0.000 description 1
- ZRAFRKODSWMDFK-UHFFFAOYSA-N 3-benzhydrylsilylpropan-1-ol Chemical compound C=1C=CC=CC=1C([SiH2]CCCO)C1=CC=CC=C1 ZRAFRKODSWMDFK-UHFFFAOYSA-N 0.000 description 1
- FMODZPDKRSPLFG-UHFFFAOYSA-N 3-benzhydrylsilylpropoxy(trimethyl)silane Chemical compound C=1C=CC=CC=1C([SiH2]CCCO[Si](C)(C)C)C1=CC=CC=C1 FMODZPDKRSPLFG-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 description 1
- LCGLNKUTAGEVQW-UHFFFAOYSA-N Dimethyl ether Chemical compound COC LCGLNKUTAGEVQW-UHFFFAOYSA-N 0.000 description 1
- PXGOKWXKJXAPGV-UHFFFAOYSA-N Fluorine Chemical compound FF PXGOKWXKJXAPGV-UHFFFAOYSA-N 0.000 description 1
- YIVJZNGAASQVEM-UHFFFAOYSA-N Lauroyl peroxide Chemical compound CCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCC YIVJZNGAASQVEM-UHFFFAOYSA-N 0.000 description 1
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 description 1
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical class [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 1
- IMIRTMYIIZODPG-UHFFFAOYSA-N [2-(benzotriazol-2-yl)-4-methylphenyl] 2-methylprop-2-enoate Chemical compound CC(=C)C(=O)OC1=CC=C(C)C=C1N1N=C2C=CC=CC2=N1 IMIRTMYIIZODPG-UHFFFAOYSA-N 0.000 description 1
- 229960000583 acetic acid Drugs 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 150000001412 amines Chemical class 0.000 description 1
- 201000009310 astigmatism Diseases 0.000 description 1
- QRUDEWIWKLJBPS-UHFFFAOYSA-N benzotriazole Chemical compound C1=CC=C2N[N][N]C2=C1 QRUDEWIWKLJBPS-UHFFFAOYSA-N 0.000 description 1
- 239000012964 benzotriazole Substances 0.000 description 1
- 235000019400 benzoyl peroxide Nutrition 0.000 description 1
- 238000009835 boiling Methods 0.000 description 1
- 239000000460 chlorine Substances 0.000 description 1
- 229910052801 chlorine Inorganic materials 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 125000000582 cycloheptyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- 125000000113 cyclohexyl group Chemical group [H]C1([H])C([H])([H])C([H])([H])C([H])(*)C([H])([H])C1([H])[H] 0.000 description 1
- XJOBOFWTZOKMOH-UHFFFAOYSA-N decanoyl decaneperoxoate Chemical compound CCCCCCCCCC(=O)OOC(=O)CCCCCCCCC XJOBOFWTZOKMOH-UHFFFAOYSA-N 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- USIUVYZYUHIAEV-UHFFFAOYSA-N diphenyl ether Chemical compound C=1C=CC=CC=1OC1=CC=CC=C1 USIUVYZYUHIAEV-UHFFFAOYSA-N 0.000 description 1
- POLCUAVZOMRGSN-UHFFFAOYSA-N dipropyl ether Chemical compound CCCOCCC POLCUAVZOMRGSN-UHFFFAOYSA-N 0.000 description 1
- 210000000871 endothelium corneal Anatomy 0.000 description 1
- 229940052303 ethers for general anesthesia Drugs 0.000 description 1
- 229940093476 ethylene glycol Drugs 0.000 description 1
- 239000002360 explosive Substances 0.000 description 1
- 229910052731 fluorine Inorganic materials 0.000 description 1
- 239000011737 fluorine Substances 0.000 description 1
- 125000004031 fumaroyl group Chemical group C(\C=C\C(=O)*)(=O)* 0.000 description 1
- 239000012362 glacial acetic acid Substances 0.000 description 1
- 125000003187 heptyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- 238000002513 implantation Methods 0.000 description 1
- 238000001727 in vivo Methods 0.000 description 1
- 208000014674 injury Diseases 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N itaconic acid Chemical compound OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 229910052749 magnesium Inorganic materials 0.000 description 1
- 239000011777 magnesium Substances 0.000 description 1
- 229910052943 magnesium sulfate Inorganic materials 0.000 description 1
- 235000019341 magnesium sulphate Nutrition 0.000 description 1
- VHRYZQNGTZXDNX-UHFFFAOYSA-N methacryloyl chloride Chemical compound CC(=C)C(Cl)=O VHRYZQNGTZXDNX-UHFFFAOYSA-N 0.000 description 1
- OKHRRIGNGQFVEE-UHFFFAOYSA-N methyl(diphenyl)silicon Chemical compound C=1C=CC=CC=1[Si](C)C1=CC=CC=C1 OKHRRIGNGQFVEE-UHFFFAOYSA-N 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- XNTUJOTWIMFEQS-UHFFFAOYSA-N octadecanoyl octadecaneperoxoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OOC(=O)CCCCCCCCCCCCCCCCC XNTUJOTWIMFEQS-UHFFFAOYSA-N 0.000 description 1
- 125000005447 octyloxy group Chemical group [H]C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])O* 0.000 description 1
- 150000001451 organic peroxides Chemical class 0.000 description 1
- 125000001147 pentyl group Chemical group C(CCCC)* 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 239000003505 polymerization initiator Substances 0.000 description 1
- 239000004926 polymethyl methacrylate Substances 0.000 description 1
- 210000001525 retina Anatomy 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 239000000377 silicon dioxide Substances 0.000 description 1
- 239000007779 soft material Substances 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 229930192474 thiophene Natural products 0.000 description 1
- 230000008733 trauma Effects 0.000 description 1
- 239000006097 ultraviolet radiation absorber Substances 0.000 description 1
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
- C07F7/00—Compounds containing elements of Groups 4 or 14 of the Periodic Table
- C07F7/02—Silicon compounds
- C07F7/08—Compounds having one or more C—Si linkages
- C07F7/0803—Compounds with Si-C or Si-Si linkages
- C07F7/081—Compounds with Si-C or Si-Si linkages comprising at least one atom selected from the elements N, O, halogen, S, Se or Te
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S623/00—Prosthesis, i.e. artificial body members, parts thereof, or aids and accessories therefor
- Y10S623/902—Method of implanting
- Y10S623/905—Eye
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10S623/00—Prosthesis, i.e. artificial body members, parts thereof, or aids and accessories therefor
- Y10S623/902—Method of implanting
- Y10S623/905—Eye
- Y10S623/907—Method of manipulating parts of intraocular lens structure for implantation
Definitions
- the present invention relates to monomers useful in the manufacture of biocompatible medical devices. More particularly, the present invention relates to aromatic-based silyl monomers capable of polymerization alone or copolymerization with other monomers. Upon polymerization or copolymerization, the subject monomers form polymeric compositions having desirable physical characteristics and refractive indices useful in the manufacture of ophthalmic devices.
- intraocular lens intraocular lens
- an intraocular lens is implanted within an eye at the time of surgically removing the diseased or damaged natural lens, such as for example, in the case of cataracts.
- the preferred material for fabricating such intraocular lens implants was poly(methyl methacrylate), which is a rigid, glassy polymer.
- Softer, more flexible IOL implants have gained in popularity in more recent years due to their ability to be compressed, folded, rolled or otherwise deformed. Such softer IOL implants may be deformed prior to insertion thereof through an incision in the cornea of an eye.
- more flexible IOL implants as just described may be implanted into an eye through an incision that is much smaller, i.e., less than 4.0 mm, than that necessary for more rigid lOLs, i.e., 5.5 to 7.0 mm.
- a larger incision is necessary for more rigid IOL implants because the lens must be inserted through an incision in the cornea slightly larger than the diameter of the inflexible IOL optic portion. Accordingly, more rigid IOL implants have become less popular in the market since larger incisions have been found to be associated with an increased incidence of postoperative complications, such as induced astigmatism.
- silicones In general, high water content hydrophilic acrylics, or "hydrogels,” have relatively low refractive indices, making them less desirable than other materials with respect to minimal incision size. Low refractive index materials require a thicker IOL optic portion to achieve a given refractive power. Silicone materials may have a higher refractive index than high- water content hydrogels, but tend to unfold explosively after being placed in the eye in a folded position.
- Low glass transition temperature hydrophobic acrylic materials are desirable because they typically have a high refractive index and unfold more slowly and more controllably than silicone materials.
- low glass transition temperature hydrophobic acrylic materials which contain little or no water initially, may absorb pockets of water in vivo causing light reflections or "glistenings.”
- Soft, foldable, high refractive index, high elongation polymeric compositions of the present invention are produced through the polymerization or copolymerization of aromatic-based silyl monomers.
- the subject monomers are synthesized through a multi-step reaction scheme.
- the polymeric compositions produced from the silyl monomers have ideal physical properties for the manufacture of ophthalmic devices.
- the polymeric compositions of the present invention are transparent, of relatively high strength for durability during surgical manipulations, of relatively high elongation, of relatively high refractive index and are biocompatible.
- the subject polymeric compositions are particularly well suited for use as intraocular lens (lOLs) implants, contact lenses, keratoprostheses, corneal rings, corneal inlays and the like.
- lOLs intraocular lens
- Preferred aromatic-based silyl monomers for use in preparing the polymeric compositions of present invention have the generalized structure represented by Formula 1 below,
- R is a polymerizable group
- X is selected from the group consisting of C- ⁇ -10 alkyl, C ⁇ . 0 alkyloxy, C 6- 36 aryl and C 6-3 6 aryloxy
- the Ri groups may be the same or different selected from the group consisting of C ⁇ _ 10 alkyl, C 1-20 cycloalkyl, C 6-36 aryl, C 6- 36 aryl ether, C 6- 36 heterocycle, C 6-36 heterocycle with one or more substituents, C- O alkyl ether and C 6 - 36 aryloxy.
- Another object of the present invention is to provide polymeric compositions of relatively high refractive index.
- Another object of the present invention is to provide polymeric compositions suitable for use in the manufacture of intraocular lens implants.
- Another object of the present invention is to provide polymeric compositions that are biocompatible.
- Another object of the present invention is to provide polymeric compositions suitable for use as contact lens materials.
- Still another object of the present invention is to provide polymeric compositions that are economical to produce.
- the present invention relates to novel aromatic-based silyl monomers synthesized through a three-step reaction scheme.
- the subject aromatic- based silyl monomers are useful in the production of biocompatible polymeric compositions.
- the subject polymeric compositions have particularly desirable physical properties.
- the subject polymeric compositions have a relatively high refractive index of approximately 1.45 or greater and relatively high elongation of approximately 100 percent or greater. Accordingly, the subject polymeric compositions are ideal for use in the manufacture of ophthalmic
- the aromatic-based silyl monomers of the present invention are generally represented by Formula 1 below:
- R is a polymerizable group selected from the group consisting of methacrylate, acrylate, acrylamido, methacrylamido, styryl, itaconate, fumaroyl, vinyl, vinyloxy, vinyl carbamate and vinyl carbonate;
- X is selected from the group consisting of C 1 - 10 alkyl such as for example but not limited to methyl, propyl or heptyl, C ⁇ -10 alkyloxy such as for example but not limited to ethyloxy, butyloxy or octyloxy, C 6- 3 6 aryl such as for example but not limited to phenyl or naphthyl and C 6 - 36 aryloxy such as for example but not limited to phenyloxy or naphthyloxy; and the R-i groups may be the same or different selected from the group consisting of C-M O alkyl such as for example but not limited to methyl, propyl or pentyl but preferably propyl for increased
- aromatic-based silyl monomers of the present invention include for example but are not limited to 1- methacryloyloxypropyldimethylphenylsilane, 1 - methacryloyloxypropyldiphenylmethylsilane and 1- methacryloyloxypropyltriphenylsilane.
- Aromatic-based silyl monomers of the present invention may be synthesized through a three-step reaction scheme as represented in Scheme 1 below:
- One or more aromatic-based silyl monomers of the present invention produced as described above may be polymerized alone or copolymerized with other monomers.
- One or more of the subject silyl monomers may be copolymerized with one or more aromatic or non-aromatic non-siloxy-based monomers, hydrophobic monomers, hydrophilic monomers or a combination thereof to produce polymeric compositions of the present invention.
- aromatic and non-aromatic non-siloxy-based monomers useful for copolymerization with one or more aromatic-based silyl monomers of the present invention include for example but are not limited to 2- phenyoxyethyl methacrylate, 3,3-diphenylpropyl methacrylate, N,N- dimethylacrylamide, methyl methacrylate, 2-(1-naphthylethyl) methacrylate, glycol methacrylate, 3-phenylpropyl acrylate and 2-(2-naphthylethyl) methacrylate but preferably 2-(1-naphthylethyl) methacrylate for increased refractive index.
- hydrophobic monomers useful for copolymerization with one or more aromatic-based silyl monomers of the present invention include for example but are not limited to 2-ethylhexyl methacrylate, 3- methacryloyloxypropyldiphenylmethylsilane and 2-phenyloxyethyl methacrylate but preferably 3-methacryloyloxypropyldiphenylmethylsilane for increased refractive index.
- hydrophilic monomers useful for copolymerization with one or more aromatic-based silyl monomers of the present invention include for example but are not limited to N,N-dimethylacrylamide and methyl methacrylate but preferably N,N-dimethylacrylamide for increased hydrophilicity.
- one or more silyl monomers of the present invention may be polymerized or copolymerized to form crosslinked three-dimensional networks.
- one or more crosslinking agents may be added in quantities less than 10 percent weight per volume (W/V) to the silyl monomer(s), if desired, prior to polymerization or copolymerization thereof.
- crosslinking agents include but are not limited to diacrylates and dimethacrylates of triethylene glycol, butylene glycol, neopentyl glycol, hexane-1 ,6-diol, thio-diethylene glycol and ethylene glycol, trimethylolpropane triacrylate, N.N'-dihydroxyethylene bisacrylamide, diallyl phthalate, triallyl cyanurate, divinylbenzene; ethylene glycol divinyl ether, N,N'-methylene-bis-(meth)acrylamide, sulfonated divinylbenzene and divinylsulfone.
- silyl monomers within the scope of the present invention may optionally have one or more strengthening agents added thereto prior to polymerization or copolymerization thereof, preferably in quantities of less than about 80 weight percent but more typically from about 20 to about 60 weight percent.
- strengthening agents examples include cycloalkyl acrylates and methacrylates, such as for example tert-butylcyclohexyl methacrylate and isopropylcyclopentyl acrylate.
- One or more ultraviolet light absorbers may optionally be added to the subject silyl monomers prior to polymerization or copolymerization thereof in quantities typically less than 2 percent W/V.
- Suitable ultraviolet light absorbers for use in the present invention include for example but are not
- the silyl monomers of the present invention may be readily cured in cast shapes, as discussed in more detail below, by one or more conventional methods. Such methods include for example but are not limited to ultraviolet light polymerization, visible light polymerization, microwave polymerization, thermal polymerization, free radical thermal polymerization or combinations thereof.
- One or more suitable free radical thermal polymerization initiators may be added to the monomers of the present invention.
- suitable free radical thermal polymerization initiators include for example but are not limited to organic peroxides, such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, tert-butyl peroxypivalate, peroxydicarbonate, and the like.
- organic peroxides such as acetyl peroxide, lauroyl peroxide, decanoyl peroxide, stearoyl peroxide, benzoyl peroxide, tert-butyl peroxypivalate, peroxydicarbonate, and the like.
- an initiator is employed in a concentration of approximately 0.01 to 1 percent by weight of the total monomer mixture.
- Representative ultraviolet light initiators include those known in the field such as for example but not limited to benzoin methyl ether, benzoin ethyl ether, DarocurTM 1173, 1164, 2273, 1116, 2959, 3331 (EM Industries) and lrgacurTM651 and 184 (Ciba-Geigy, Basel, Switzerland).
- the polymeric compositions of the present invention are of relatively high refractive index, relatively high elongation and relatively high clarity.
- the polymeric compositions of the present invention with the desirable physical properties noted above are particularly useful in the manufacture of ophthalmic devices such as but not limited to relatively thin, foldable intraocular lens implants, contact lenses and corneal inlays.
- lOLs having relatively thin optic portions are critical in enabling a surgeon to minimize surgical incision size. Keeping the surgical incision size to a minimum reduces intraoperative trauma and postoperative complications.
- a relatively thin IOL optic portion is also critical for accommodating certain anatomical locations in the eye such as the anterior chamber and the ciliary sulcus. lOLs may be placed in the anterior chamber for increasing visual acuity in either aphakic or phakic eyes, or placed in the ciliary sulcus for increasing visual acuity in phakic eyes.
- the polymeric compositions of the present invention have the flexibility required to allow implants manufactured from the same to be folded or deformed for insertion into an eye through the smallest possible surgical incision, i.e., 3.5 mm or smaller. It is unexpected that the subject polymeric compositions could possess the ideal physical properties described herein.
- the ideal physical properties of the subject polymeric compositions are unexpected because high refractive index monomers typically lend to polymers that have increased crystallinity and decreased clarity, which does not hold true in the case of the subject polymeric compositions.
- Step one synthesis of 3-(trimethylsilyloxy)propyldiphenylmethylsilane
- Step three synthesis of 3-acryloyloxypropyldiphenylmethylsilane
- the resulting solution was dried over MgS0 , filtered and rotovapped to a yellow oil.
- the oil was passed through a 400g silica column eluding with 70/30, 50/50 and 30/70 heptane/dichloromethane solutions (2 bed volumes each). After solvent removal, 59 g of 3-acryloyloxypropyldiphenylmethylsilane (98.6% by GC) was recovered.
- the resultant film was hydrated at room temperature overnight in borate buffered saline.
- the clear tack-free films possessed a modulus of 81 g/mm 2 , a tear strength of 77 g/mm, a % elongation of 228%, a water content of 5% and a refractive index of 1.5442.
- APDMS was added 10 parts of N,N- dimethylacrylamide, 20 parts of hexanol, 1 part of ethyleneglycol dimethacrylate and 0.5% of IrgacureTM 819 as the UV photoinitiator and 0.25% of a commercial triazole UV blocker (Aldrich Chemical Co).
- the clear solution was sandwiched between two silanized glass plates using metal gaskets and exposed to UV radiation for two hours.
- the resultant films were released and extracted in IPA for four hours, followed by air-drying and a 30 mm vacuum to remove the IPA.
- the resultant film was hydrated at room temperature overnight in borate buffered saline.
- the clear tack-free films possessed a modulus of 161 g/mm 2 , a tear strength of 64 g/mm, a % elongation of 183%, a water content of 10.5 % and a refractive index of 1.517.
- Ophthalmic devices such as but not limited to lOLs manufactured using the polymeric compositions of the present invention can be of any design capable of being rolled or folded for implantation through a relatively small surgical incision, i.e., 3.5 mm or less.
- ophthalmic devices such as lOLs typically comprise an optic portion and one or more haptic portions.
- the optic portion reflects light onto the retina and the permanently attached haptic portions hold the optic portion in proper alignment within an eye.
- the haptic portions may be integrally formed with the optic portion in a one-piece design or attached by staking, adhesives or other methods known to those skilled in the art in a multipiece design.
- the subject ophthalmic devices such as for example lOLs, may be manufactured to have an optic portion and haptic portions made of the same or differing materials.
- both the optic portion and the haptic portions of the lOLs are made of one or more polymeric compositions of the present invention.
- the IOL optic portion and haptic portions may be manufactured from differing materials and/or differing polymeric compositions of the present invention, such as described in U.S. Patent Numbers 5, 217,491 and 5,326,506, each incorporated herein in its entirety by reference. Once the particular material or materials are selected, the same is either cast in molds of the desired shape or cast in the form of rods and lathed or machined into disks.
- the disks are lathed or machined into lOLs at low temperatures below the glass transition temperature(s) of the material(s).
- the lOLs, whether molded or machined/lathed, are then cleaned, polished, packaged and sterilized by customary methods known to those skilled in the art.
- the polymeric compositions of the present invention are also suitable for use in the manufacture of other ophthalmic devices such as but not limited to contact lenses, keratoprostheses, capsular bag extension rings, corneal inlays, corneal rings or like devices.
- lOLs manufactured using the unique polymeric compositions of the present invention are used as customary in the field of ophthalmology. For example, in a surgical procedure, an incision is placed in the cornea of an eye. Most commonly, through the corneal incision the natural lens of the eye is removed (aphakic application) such as in the case of a cataractous natural lens. An IOL is then inserted into the anterior chamber, posterior chamber or lens capsule of the eye prior to closing the incision.
- the subject ophthalmic devices may be used in accordance with other surgical procedures known to those skilled in the field of ophthalmology.
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
- Materials For Medical Uses (AREA)
- Prostheses (AREA)
- Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
- Fats And Perfumes (AREA)
- Steroid Compounds (AREA)
Abstract
Description
Claims
Applications Claiming Priority (3)
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US10/003,616 US6762271B2 (en) | 2001-11-02 | 2001-11-02 | High refractive index aromatic-based silyl monomers |
PCT/US2002/032686 WO2003040152A1 (en) | 2001-11-02 | 2002-10-11 | High refractive index aromatic-based silyl monomers |
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-
2001
- 2001-11-02 US US10/003,616 patent/US6762271B2/en not_active Expired - Fee Related
-
2002
- 2002-10-11 JP JP2003542197A patent/JP2005508409A/en active Pending
- 2002-10-11 CA CA002465238A patent/CA2465238A1/en not_active Abandoned
- 2002-10-11 EP EP02786399A patent/EP1444239B1/en not_active Expired - Lifetime
- 2002-10-11 KR KR1020047006539A patent/KR20050035176A/en not_active Application Discontinuation
- 2002-10-11 WO PCT/US2002/032686 patent/WO2003040152A1/en active Application Filing
- 2002-10-11 CN CNA028219325A patent/CN1582289A/en active Pending
- 2002-10-11 DE DE60230537T patent/DE60230537D1/en not_active Expired - Lifetime
- 2002-10-11 AT AT02786399T patent/ATE418560T1/en not_active IP Right Cessation
-
2004
- 2004-05-18 US US10/848,262 patent/US20040215032A1/en not_active Abandoned
- 2004-05-18 US US10/847,941 patent/US6846897B2/en not_active Expired - Fee Related
- 2004-05-18 US US10/848,308 patent/US6881809B2/en not_active Expired - Fee Related
- 2004-05-18 US US10/848,305 patent/US7132494B2/en not_active Expired - Lifetime
Non-Patent Citations (1)
Title |
---|
See references of WO03040152A1 * |
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US6881809B2 (en) | 2005-04-19 |
US20040215032A1 (en) | 2004-10-28 |
US6846897B2 (en) | 2005-01-25 |
CN1582289A (en) | 2005-02-16 |
EP1444239B1 (en) | 2008-12-24 |
ATE418560T1 (en) | 2009-01-15 |
US20040230023A1 (en) | 2004-11-18 |
DE60230537D1 (en) | 2009-02-05 |
US20040215156A1 (en) | 2004-10-28 |
JP2005508409A (en) | 2005-03-31 |
US20040210023A1 (en) | 2004-10-21 |
US7132494B2 (en) | 2006-11-07 |
US20030105255A1 (en) | 2003-06-05 |
KR20050035176A (en) | 2005-04-15 |
US6762271B2 (en) | 2004-07-13 |
WO2003040152A1 (en) | 2003-05-15 |
CA2465238A1 (en) | 2003-05-15 |
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